Process for decolorizing hydrocarbon oil



Aug. 7, 1945. w. A. L LANDE, JR I 2,381,293

PROCESS FOR DECOLORIZING HYDROCARBON OILI Original Filed March 28, 1942 1 Raw Clay r Roll Crusher Cooler Roller Mill Sioray e Calahiny v N Reject v Inventor flitest r -13 A. La Lands J1:

Patented Aug. 7, 1945 UNITED STATES PAT 2,381,293 DECOLORIZING HYDRO- PROCESS FOR 2,381,293 ENT' OFFICE CARBON OIL William A. La Lande, Jr., Upper Darby, 1a., assignor to Attapulgus Clay Company, Philadelphia, Pa., a corporation of Delaware Original application March 28, 1942, Serial No. 436,630. Divided and this application April 28,

1944, Serial No. 533,237

6 Claims. (01. 196-41) The present invention relates to a process for increasing the adsorptive capacity, and particu- In accordance with the present invention, I

' have found that the adsorptive capacity, and parlarly the decolorizing or bleaching efiiciency of argillaceoussubstances such as fullers earth of the Georgia-Florida type.

This application is a division of my application Serial Number 436,630, filed March 28, 1942, now Patent 2,363,876, issued November 28, 1944,

In the production of granular fullers earth for use in the treatment of petroleum products, and especially for decolorization oflubricating oils and waxes, it 'has been conventional practice to dry the raw fullers earth, crush the dried earth,

screen the crushed material to obtain granular particles of the desired size, for example, 3060 mesh, and thereafter heat or calcine the granular particles at temperatures of the order of from 900 F. to 1200" F., prior to utilizing theearth as a decolorizer. Fuller's earth produced in this manner, and employed in large quantities for decolorizing hydrocarbon oils and waxes; has: an

-' average volatile content (mostly water) of the order of from 3.5% to 4% by Weight, a volume weight of the order of from 30 to 33 lbs. per cubic foot, and a 'decolorizing efiiciency; arbitrarily designated as 100% on both the weight and vol- .ume basis.

The decolorizing efiicjency of types of iullers earths may be imprgved by arprocess wherein the fuller'searth containing sumcient.

water to render it plastic is subjected to a grinding, kneading and mixing action under substantial pressure, for example, of the order of from 400 to 1200 pounds per square inch, and then I extruded through a die-plate provided with plurality of orifices.

The earth is then dried,

ticularly the decolorizin'g' efliciency of fullers earths for hydrocarbon oils maybe markedly increased in a relatively simple and inexpensive manner. More specifically, in accordance with my invention, I have been able to increase the decolorizing efliciency of fullers earth upon the volume basis to a very substantial extent, and usually at thesame time increase the decolorizing efficiency upon the weight basis. Further- .more, I have been able to effect an advantageous increase in volume weight (lbs/cu. ft.) of the fullers earth treated in accordance with my process. By thus increasing the volume weight, the decolorizing capacity of a filter of given volume may be increased, fo'r'example, by 20 to 40%.

My invention is particularly applicable to the treatmentof those fullers earths, which, upon beingsubjected to grinding, kneading, mixing and extrusion under substantial pressure in" watermoist or plastic conditions, and thereafter being dried, screened and calcined, will exhibit a deground, screened and calcined to produce, for example, a granular earth of -60 mesh, which has improved decolorizing properties for mineral oils. Tests upon numerous samples of 'fullers earths which respond to increase in decolorizing efficiency when processed in the manner last above referred to, indicates thatthe 'decolorizing. eiilciency upon a weight basis is markedly improved, that the decolorizing efliciency upon a .volume basis is also improved, but to a lesser degree reacts alkaline in aqueous solution, the mixture is extruded at elevated pressure in a suitable extrusion machine. The extruded material. is dried than upon the weight basis, and that the volume weight of the processed earth (e. g. pounds per cubic foot) is substantially lower'than that of samples of the respective fullers earths not so processed. Typical of the properties-of a fullers earth before and after so processing, arev the following:

Before- After Decolorizing efliciency (weight basis) p er cent 100 124 Decolorizhglg emciency (volume basis).....do 100. .118 Volume w ght (calcined) .lbs per cu. it 31-32 27-30. 5

and then reduced to granular particles of desired size by crushing and screening, and the granular particles are finally heated or calcined at tem-' peratures of the order of from 200 F. to 1400710,

and preferably at temperatures of from 800 F. to

1200 F., prior to use as a de'colorizing medium for hydrocarbon oils.- The'quantity of alkaline agent employed may range from 0.1% to about 1.175%

byfweight,-based upon volatileefre fuller's earth,

and is preferably of the order of from 1.00 to 1.50% by weight.- Since the volatile content of fullers earth varies considerably. with the source of the material, the quantity of water to be used in making up the alkaline solution to be admixed with the earth likewise must be varied, in order that the total volatile contentmf the earth be kept within the, desired limits, 1. e., 45% to 60% by weight, during the mixing and extrusion operation. In general, the concentration'of alkaline agent in the aqueous solution to be mixed with the iullersearth is of the order of from 1% to 8% by weight. By volatile content or volatile shows diagrammatically a system suitable for matter is meant those constituents of Iuller's carrying out my process.

earth which are volatilized or driven off by heat- Raw fullers earth or clay of the type obtained ing the earth for a period of 20 minutes at a from the Georgia-Florida fullers earth deposits temperature of substantially 1800 F. The mixand containing natural moisture (45% to 55%) is ing operation may be accomplished in any suitpassed from storage vessel l'to'the roll crusher able device capable of efiecting intimate contact Z'wherein the lumpy earth is reduced to relatively between the fullers earth and the solution of flat fragments which may be readily handled in alkaline agent, for example, a pug mill. The exthe pug mill 3. The pug mill 3 consists of a hous- .trusion operation is preferably carried out in a ing and a longitudinal shaft 4 having a plurality continuous screw extrusion machine in which a of spirally disposed paddles 5 adapted to intimixing, grinding, and shearing action under elemately mix the earth while advancing it toward vated pressure may be obtained. The time rethe discharge end of the housing. The shaft may quired for mixing and extrusion is generally a be rotated at a suitable speed by a motor or other function of the type of device utilized, and in all source of power not shown. In the pug mill the cases must be sufficient to permit a thorough earth is intimately admixed with the alkaline incorporation of the alkaline solution in the agent introduced in solution through line 6, the fullers earth. Periods of the order of from 10 quantity of agent being of the order of 0.1% to to 15 minutes or longer may be employed. The 1.75% by weight, based on the volatile-free earth, temperature at which mixing and extrusion is and preferably about 1% by weight. Depending carried out may range from atmospheric to about upon the initial moisture of the raw earth, the 200 F., and is preferably of the order of from concentration of the alkaline solution introduced 70 F. to 100 F. While it is preferred to employ through line 6 is adjusted to give a total volatile raw fullers earth containing natural moisture content in the earth of the order of from 45 to as the starting material, earths which have been 60% by weight. d preferably of the Order driedand rewetted may also be utilized. When from 50 to 55% by weight. if necessary, water employing a continuous extrusion press to obtain may be added to the earth in the pug mill by a mixing, grinding=and shearing action under means of line I.

elevated pressure, one may prepare the charge for Upon discharge from the pug'mill 3, the plastic the press in the following manner. The raw earth of proper'moisture contnt'and containing, fullers earth, in the form of lumps, may be subfor example, 1% of alkalineagent thoroughly disjected to a preliminary crushing to reduce the persed therein, is introduced into an apparatus lumps, and the reduced earth may be mixed dicapable of exerting a mixing, grinding, and shearrectly with the solution of alkaline agent, for ing action thereupon, preferably under elevated example, in a pug mill, care being taken to adjust pressure. The apparatus, in the present instance,

the concentration of the solution so that the water is shown as an auger-type, continuous extrusion content thereof plus the natural water content p es Comprising a housing Darrel Bprovided of the earth will give a plastic material havin with a rotatable screw 9 and a die plate 10 at the volatile content between and60% by weight. discharge d 0 t ousing. The die Plate W Among the chemical agents reacting alkaline 40 is provided with a plurality of orifices of suitable inaqueous solution which may be employed in e and Shape, Such? orifices generally having a accordance with my invention are the hydroxides, diameter of from about one-e th to bo t S oxides, peroxides, carbonates, bicarbonates, seceighths of an inch. The plastic earth containin ondary and tertiary phosphates, silicates, sul the alkaline age n du into e housing fites and sulfides of Na, K, Li, and NH4 which are is subjected therein to an intensive mixing, grindsoluble in water to substantial extent. Because ing. and shearing act by means of the screw 9; of their availability, effectiveness, and non-corand is finally extruded through the orifices of the rosive properties, the alkali metal hydroxides, and die plate I'll at elevated pressures of the order of particularly sodium hydroxide are preferred. from 400 to 00 pou s D Square inch,

Other alkaline reacting substances which may er. he mo t, extruded earth dischar ed be employed are the alkoxides and phenolates of through the orifices of the die p e is then strong bases; alkali metal hydrosulfldes and polypassed t h a dr I I whe e it is ri d. pr sulfldes; calcium and barium hydrosulfides and erably at temperatures of from 250 F. to 300 F.. polysulfldes; soluble magnesium, calcium, and to thedesired volatile content, for example, 15% barium salts of the weak acids; alkali metal aluby weight. The heated earth frpm the. drier Ii minates, zincates, plumbites, arsenites, arsenates, is cooled in tank I2 and passed to e T0119! mill antimonites, stannites, stannates, chromites, l3, wherein the dried earth is reduced to granular manganates, phosphites, hypophosphites, hydroparticles. The'granular material from mill I3 is sulfites, thiosulfates, hypochlorites, hydrogen sulthereafter screened in screen [4, and that porfites; amides of metals forming soluble strong tion having the desired paaticle size, for example,

bases; quaternary bases such as tetraalkyl am- 30 to 60 mesh, is either pa sed to storage or calmonium hydroxides, tetra-aryl ammonium hy cined at elevated temperatures of the order oi droxides, and mixed alkylaryl ammonium hyfrom 200 F. to 1400 F., and preferably at temdroxides; hydrazine, hydroxylamine, urea; and B5 peratures of from 800 F. to 1200" F. Dust.or fines, other organic bases. While, in general, ,it is de-. resulting from the milling and screening operasirable to employ aqueous solutions of alkaline tions (designated as rejects), may be returned agents, advantageous results may be obtained by t0 the 1 81 1? t0 the extrusion Press .f utilizing aqueous alcoholic solutions, or solutions further processing."--. Or, such fines, being of themcontaining small amounts of wetting agents such solves ofimprove'd adsorptive efllciency, may be as fatty acid soaps, water-soluble sulfonic acid employed-in various processes, such as contact soaps, sulfonated alcohols, and. the like, in addi decolorization of hydrocarbon oils, or as catalysts tionto th alkaline a ent, a or catalyst carriers, and the like. Oversize par- My invention may be further illustrated with ticles from screen may be returned to the roller reference to the accompanying drawing, which mill l3 and reduced to particles predominantly of wei ht .and volume basis.

the desired size, and thereafter screened as above to show the advantages of my process over those volume of filtrate of 6 N. P. A. color thus obtained, when compared with the volume of filtrate of the same color obtained by filtration through commercial fullers earth, is indicative of the decolemployed heretofore, the following examples are 5 orizing efiiciency of the treated earth.

. Extrusion Product Example Efficiency V. M. Time, V. M. Ampere Thruput, V. M. Vol. wt. wt. min. wt. load oz./min. burned burned wt. VOL 1 1. Commercial iuller's earth"... L 3. 5 31. 7 100.0 100.0 2. Raw fullers earth 53. 5 15 53. 5 3. 5 34.6 3.4 29.6 121.2 114. 3 3. Raw iulier's earth+0.25% NaOH.. 53. 6 15 53. 6 3. 5 33. 5 3.8 32. 1 125.0 125. 7 4. Raw iu ler's earth-{050% NaOEL. 53. 8 15 53. 8 3. 5 32.8 3. 6 32.8 123. 4 126. 4 5. Raw iuiler's earth+0.75% NaH.. 54.0 15 54.0 3.5 33.3 3.7 32.8 124. 7 128.2 0. Raw iullers earth+1.07 NaOH 53. 4 15 53. 4 3. 32. 3 3. 7 33. 8 124. 2 131. 7 7. Raw in iler's earth-+1.25 o Na0H 54. 2 g 51. 2 3. 5 38. 8 3.4 34.3 127. 3 137.0 8. Raw fuilers earth-+1.50 Na0H 54. 3 15 54. 3 3. 5 38. 6 3. 5 35. 4 124.2 137. 9 9. Raw iuller's earth-k115i NaOH.. 53. 4 p 15 53. 4 3. 5 32. 7 3. 7 36. 3 120. 5 137. 0 10. Raw fuilets earth+2.0% NaOH--. 53.5 15 53. 5 3.5 31.5 4.0 36.2 116.2 132.2 11. Raw fuilers earth+1.0 n NagCO 53. 7 15 53. 7 3. 5 36. 6 3. 8 32. 5 122. 5 125. 2 12. Raw iullers earth+l.0 o LlOH v53. 5 15 53.5 3. 5 34.8 3.0 33. 1 123.2 128.4 13. Raw iullers e31'th+1.0% NH4OH. 53. 7 15 53. 7 3. 5 14. 3 4. 0 30. 2 127. 0 120. 7 14. Raw fuller's earth+1.0% NaHCO; 53.8 15 53.8 3.0 18.9 3.9 30. 7 128. 2 123.3 15. Raw iuller's earth+1.0'7 NaaHPOn. 53.8 15 53. 8 2. 5 33. 5 3. 2 31. 3 123.0 120- 7 16. Raw iu cr's earth+l.0% NaiP04. 53.8 15 53.8 3.5 36.4 4.0 31.2 128.4 125.4 17. Raw in ers earth+1.0'7 Ne sio 53. 7 15 53. 7 3. 5 31. 6 3. 5 31. 0 128.8 125. 2 18. Raw :u er's earth-H0 a N815. 53. 4 15 53. 4 2. 6 10. 9 3. 9 32. 7 125.1 127. 4 19. Raw iulUer's earth+1.0% NBiSO 53. 2 15 53. 2 2. 5 7. 4 4. 3 31. 4 124. 2 122. 0

2 presented. It is to be understood that such examples are merely illustrative and are not to be considered as limiting the scope of myinvention. In the table are shown the results obtained by treating raw fullers earth from the Attap'ulgus, Georgia, fullers earth deposits, in the presence and in the absence 'of added chemical agents.

.For purposes of comparison there are included ex- 'amples of commercial Georgia-Florida fulleris earth, and Georgia-Florida fullers earth hu ged in the presence and in the absence of chemical agents and-then extruded. A

Commercial fuller's earth (Example 1) was pro- It will be seen from Examples 3 to 9 and 10 to 19 that treatment of fullers earth with. chemical agents reacting alkaline in aqueous solution results in a marked increase in decolorizing efiiciency, both on a weight and volumebasis, as well as an increase in volume weight in the majority of duced by drying raw fullers earth (V. M.--48%),

of earth varying with volatile content thereof and 'with'the effect of the chemical agent upon the earth. 1n all cases, the earth resultingfrom the pugging and extrusion operations was dried, ground and screened to 30 to 60 mesh, calcined or burned at 900v F. for 20 minutes, and then tested for volatile matter (V. M.) volume weight (lbs/cu. ft.) and decolorizing efilciency on both c iency .was' determined by solution filtration of Pennsylvania A Cylinder Stock through a given stant load. 1. e., about 3.5 amperes, the thruput The decolorizing efllthe samples treated. Pugging raw fuller's earth with less than about 2% by weight of an alkaline agent, followed by extrusion (Examples 3 to 9 and 10 to 19), produces a substantial increase in volume weight, as well as a great improvement in decolorizing efficiency (particularly on a volume basis), as compared with commercial i'uller's earth (Example 1). or raw fullers earth which has simply been pugged with water and then extruded (Example 2). It will be noted that the weight efliciency of the treated earth in Example 10, using 2% NaOH, has fallen belowthat of the water-extruded earth (Example 2). Such decrease is substantial and undesirable, and it is therefore evident that the quantity of alkaline agent should be maintained below 2%, and preferably not higher than about 1.75%, in order to maintain the weight efliciency at least equal to and the volume efliciency greater than the corresponding efllciencies of water-extruded fullers earth.

To further compare the efficiencies, on both the weight and volume basis, of water-extruded fuller's earth and earth containing different quantitles of an alkaline reagent, 1. e., NaOH, the 101-, lowing examples are presented. .The processing and testing methods were identical with those described with reference to the examples given hereinbefore, with the exception that theraw Georgia-Florida type fullers'earth was taken from a diflerent batch than that employed in weight of earthat 135 to 6 N. P. A. color. The the previous examples.

. I 4 o Earth samples 55? fggg NeOH NaOH NaOH m h Na K c extruded extruded extruded extruded extruded Extrusion: Volatile matter (wt. 54. 2 53.8 53. 4 54. 0 53. 5 54. 0 Product (calcined 900 F.): Volatilematter A 2.4 Y 2.1 i 1.7 1 2.3 Y 2.4 1.9 Volumeweight bs. cu. it.)..- 31.7 29.3 32.0 33. l 35. 1. 47.3 72. 5 Decoloriziug efllciency: Weight%efliciency. v 126 120 104 28 None Volume efliciency 100 117 128 114 42 None From the above examples, it is apparent that extrusion of the earth containing 1% NaOI-I produced a substantial increase in volume efliciency over that of the water-extruded earth, but that with earth's containing 2% or more of NaOH, the efllciencies decreased.

The argillaceous substances of the fullers earth type produced in accordance with my invention and having substantially improved adsorptive properties may be employed in the, decolorization of hydrocarbon oils, petrolatum, and hydrocarbon wax. Such improved argillaceous substances may also be utilized in the treatment of petroleum distillates for the removal of sulfur compounds, gum, and color-forming constituents, as well as catalysts or catalyst carriers in the cracking, reforming, polymerization, oxidation, hydrogenation, and dehydrogenation of hydrocarbon oils, waxes, and gases.

While, herein, reference has been made to the production of granular particles particularly of alkaline agent, and thereafter dried, reduced to granular particles, and calcined.

2. A process for decolorizing hydrocarbon oil,

which comprises treating said oil with Georyia- I which comprises treating said oil with Georgiahydroxide, and thereafter dried, reduced to gran- -60 mesh size, it is to be understood that the.

production of particles of any desired size is within the scope of this invention. Depending upon the use to which my improved argillaceous substances are to be put, the particle size may vary to a considerable extent. For example, the particles may be of the following mesh sizes: 180-300,. 100-200, 60-90, 50-180, 30-60, 15-60, 15-30, 12-30,

1. A process for decolorizing hydrocarbon oil,-

which comprises contacting said oil with Georgia- Florida type fuller's earth which has been extruded in a plastic state at elevated pressure in admixture with from 0.1% to'1.'75% by weight,

based upon volatile-free earth, of a water-soluble ular particles, and calcined.

4. A process for decolorizing hydrocarbon oil, which comprises treating said 011 with Georgia- Florida type fullersearth which has been extraded in a plastic estate at elevated pressure in admixture with from 1% to 1.5% by weight, based upon volatile-free earth, of an alkali metal hydroxide, and thereafter dried, reduced to granular particles, and calcined.

5. A process for decolorizing hydrocarbon oil,

'which comprises treating said oil-with Georgia- Florida type fullers earth which has been extruded in a plastic state at elevated pressure in admixture with from 0.1% to 1.75% by weight, based upon volatile-free earth, of sodium hydroxide, and thereafter dried, reduced to granular particles, and calcined.

6. A process for decolorizing hydrocarbon oil, which comprises treating said oil with Georgia- Florida type fullers earth which has been'extruded in a plastic state at elevated pressure in admixture with about 1% by weight, based upon volatile-free earth, of sodium hydroxide, and

, thereafter dried, reduced to granular particles,

and calcined.

WILLIAM A. LA LANDE, Ja. 

